CN100422240C - Organosilicate polyer and insulating film therefrom - Google Patents
Organosilicate polyer and insulating film therefrom Download PDFInfo
- Publication number
- CN100422240C CN100422240C CNB028018273A CN02801827A CN100422240C CN 100422240 C CN100422240 C CN 100422240C CN B028018273 A CNB028018273 A CN B028018273A CN 02801827 A CN02801827 A CN 02801827A CN 100422240 C CN100422240 C CN 100422240C
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- CN
- China
- Prior art keywords
- organic
- polymer
- silane compound
- silane
- acid ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920000642 polymer Polymers 0.000 claims abstract description 92
- 239000000126 substance Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 37
- 230000007062 hydrolysis Effects 0.000 claims abstract description 20
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- -1 silicic acid ester Chemical class 0.000 claims description 116
- 229910000077 silane Inorganic materials 0.000 claims description 85
- 238000002360 preparation method Methods 0.000 claims description 53
- 235000012239 silicon dioxide Nutrition 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 38
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000003960 organic solvent Substances 0.000 claims description 23
- 229910052731 fluorine Inorganic materials 0.000 claims description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 17
- 238000009833 condensation Methods 0.000 claims description 17
- 230000005494 condensation Effects 0.000 claims description 17
- 239000011737 fluorine Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229920000620 organic polymer Polymers 0.000 claims description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 238000003747 Grignard reaction Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 229910052802 copper Chemical group 0.000 claims description 6
- 239000010949 copper Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- 229910000765 intermetallic Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 239000013543 active substance Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 230000014509 gene expression Effects 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical group [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 239000007859 condensation product Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000003989 dielectric material Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229960004132 diethyl ether Drugs 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 208000034189 Sclerosis Diseases 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- ZDOBWJOCPDIBRZ-UHFFFAOYSA-N chloromethyl(triethoxy)silane Chemical compound CCO[Si](CCl)(OCC)OCC ZDOBWJOCPDIBRZ-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000001282 organosilanes Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- AWBIJARKDOFDAN-UHFFFAOYSA-N 2,5-dimethyl-1,4-dioxane Chemical compound CC1COC(C)CO1 AWBIJARKDOFDAN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/312—Organic layers, e.g. photoresist
- H01L21/3121—Layers comprising organo-silicon compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
- H01L21/02216—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
Abstract
The present invention relates to a low dielectric substance essential for a next generating electrical device such as a semiconductor device having high performance and high density, and particularly to a process for preparing a low dielectric organosilicate polymer, a hydrolysis condensation product of a carbon-bridged oligomer; a process for manufacturing an insulating film using an organosilicate polymer prepared by the process; and an electrical device comprising an insulating film prepared by the process. The organosilicate polymer prepared according the process of the present invention is thermally stable, and has good film-forming properties, excellent mechanical strength and crack resistance, and the film manufactured therefrom has excellent insulating properties, film uniformity, dielectric properties, crack resistance, and mechanical strength.
Description
Technical field
The present invention relates to have high-performance and high-density, inferior generation electrical part such as the necessary dielectric materials of semiconducter device.More specifically, the present invention relates to the preparation method of organic silicic acid ester polymer, the organic silicic acid ester polymer is heat-staple and has good film forming properties and excellent physical strength and anti-crack property, the present invention and relate to insulating film is made in use by the organic silicic acid ester polymer of this method preparation method.
Background technology
Semi-conductor industry is in integrated circuit (IC)-components, and is in storer and logic chip, just integrated and develop towards increasing device complexity, require to shrink geometrical dimension and having a higher assembly of large size density more.This number of levels purpose that causes connecting up increase and the reduction of wire distribution distance with the increase wiring density.Present forward position logic processor has the 7-8 level of high density interconnect, and the interconnection line width is predefined in about 2004 and is reduced to 0.1 μ m.
When device size is retracted to less than 0.25 μ m, because resistance capacitance coupled propagation delay, cross-talk noise and power dissipation become remarkable.Littler linear dimension increases the resistivity of plain conductor, and narrow intermetallic space increases the electric capacity between the plain conductor.Therefore, although the switching speed of device can increase when characteristic dimension reduces, interconnect delay becomes the major portion of total delay and limits overall chip performance.Therefore, for preparation has high-speed chip, should use the dielectric materials that has low-resistance conductor and have low-k.In addition, the use of dielectric materials can reduce power dissipation and cross-talk noise significantly.
Recently, several manufacturers of semiconductor devices have used the copper wiring with high conductivity to replace conventional aluminium wiring, with demonstrate improvement in performance be 20% or bigger test products put goods on the market.What be used to interconnect, show the conversion of the novel material use of low-k performance recently.If the dielectric film between the interconnection layer of unicircuit can use these materials, then to operating speed to influence meeting identical with the influence that is caused by the conversion from aluminium to the copper technology.For example, about 2.5 if the specific inductivity of dielectric materials changes to from 4.0, the IC operating speed can improve about 20%.
The interbed dielectric materials that is used for semiconductor device mainly is SiO
2, it generally use chemical vapor deposition (CVD) form with bear with form dielectric condition under relevant various process operations.The silicon thermal oxidation film, it has minimum specific inductivity, and its specific inductivity is about 4.0.Attempted by in sedimentary mineral membrane, introducing fluorine atom to reduce specific inductivity by CVD.Yet the introducing of a large amount of fluorine atoms reduces chemistry and thermostability, makes the specific inductivity that reaches in true enforcement be about 3.5.Fluorinated oxide can provide direct short-term solution, may require the conversion to the novel type insulating material with 3 following specific inductivity.
One class candidate material is an organic polymer, and the specific inductivity of some of them is less than 3.0.The known fluorine of introducing in such organic polymer further reduces specific inductivity.Yet most of organic polymers do not have physical and chemical performance, particularly thermostability and the mechanical property (back end of line that is enough to bear in 400~450 ℃ of scopes is made temperature) of chip-scale semiconducting insulation body requirement.Organic polymer is seldom stablized under greater than 450 ℃ temperature.They also have lower glass transition temperatures and therefore their elasticity significantly reduction at high temperature, and they have very high coefficient of linear expansion.Owing to temperature during and the packaging technology integrated at semiconducter IC rises to 450 ℃, but the low thermal stability that therefore obtains and the reliability of elasticity and high coefficient of linear expansion deterioration device.
Recently, be to solve the thermal stability problems of organic polymer, the exploitation of the organic silicic acid ester polymer of collosol craft occurred using.Especially, advised the organic SOG (spin-coating glass) of specific inductivity in about 2.7~3.3 scopes as interlayer dielectric, wherein the side chain of organic constituent (alkyl such as methyl) is bonded on the back key chain of siloxane bond.Yet the organic silicic acid ester polymer shows the mechanical property of going on business.For example, unless during technology film extremely thin (usually<1 μ m), poly-methyl silsesquioxane shows that the crack forms, and shows because the low mechanical modulus that alkyl is introduced.
People such as Miller have reported by introducing the method that small amount of polymer substituting group such as polyimide come toughness reinforcing silicious sesquioxane material system.The method of mixing the inorganic fine particle powder is known as the method for improving organosilicon acid esters physical strength.Although proposed various systems, need have suitable low-k and suitable physical chemical property, as the material of IC device interlayer dielectric of future generation.
Summary of the invention
Therefore, consider that prior art problems carries out the present invention, the preparation method who the purpose of this invention is to provide the dielectric materials that is used for very low dielectric interbed wiring insulating film, this insulating film can make semiconducter device speed higher, reduce watt consumption, and reduce the cross-talk between the metal line significantly.
Another object of the present invention provides the preparation method of the organic silicic acid ester polymer with excellent in resistance crack property, physical strength, film forming properties and dielectric properties, and the manufacture method of the insulating film that comprises the polymkeric substance for preparing according to this method is provided.
For reaching these purposes, the invention provides two kinds of methods of preparation organic silicic acid ester polymer.
First method comprises:
A) provide the organo-metallic silane compound of representing by following chemical formula 1;
B) cause the grignard reaction of independent a) the organo-metallic silane compound of representing by chemical formula 1, with the silane low polymer of preparation carbon bridge joint and remove the metallic compound by product;
C) in organic solvent, mix b) silane low polymer of carbon bridge joint, and to wherein adding entry and catalyzer to cause that hydrolysis and condensation are with preparation organic silicic acid ester polymer;
Chemical formula 1:
R
1 pR
2 3-pSiR
3MX
Wherein
R
1Be that hydrogen, fluorine, aryl, vinyl, allyl group or fluorine replace independently or unsubstituted linearity or branching C
1-4Alkyl;
R
2Be chlorine, acetoxyl group, hydroxyl or linearity or branching C independently
1-4Alkoxyl group;
R
3Be C
1-6Hydrocarbon;
M is magnesium, mercury or copper;
X is a halogen;
P is the integer of 0-2.
In addition, second method comprises:
A) provide the organo-metallic silane compound of representing by above chemical formula 1;
B) cause the grignard reaction of following material:
I) a) the organo-metallic silane compound of representing by chemical general formula; With
Ii) silane compound or silane low polymer
With the silane low polymer of preparation carbon bridge joint with remove the metallic compound by product;
C) in organic solvent, mix b) silane low polymer of carbon bridge joint, to wherein adding entry and catalyzer to cause that hydrolysis and condensation are with preparation organic silicic acid ester polymer.
The present invention also is provided for forming the composition of semiconducter device insulating film, and this insulating film comprises the organic silicic acid ester polymer by one of above method preparation, the present invention and the method for the manufacturing semiconducter device insulating film that comprises coating and curing composition is provided.
Particularly, the present invention's composition of being used to form the semiconducter device insulating film comprises:
A) the organic silicic acid ester polymer for preparing by every kind of organic silicic acid ester polymer preparation method;
B) organic solvent.
The composition that forms insulating film can further comprise:
C) one or more are selected from following additive: organic molecule, organic polymer, organic branch-shape polymer, colloid silica, aerosol, dried colloidal sol and tensio-active agent.
The present invention also provides the manufacture method of semiconducter device insulating film, comprising:
A) provide the organic silicic acid ester polymer for preparing by every kind of organic silicic acid ester polymer preparation method;
B) organic silicon ester polymkeric substance of dissolving and solubilising additive in solvent when needed in solvent;
C) the organic silicon ester polymers soln of coating on semiconductor device substrates;
D) the dry insulating film that applies with curing,
The present invention also provides the semiconducter device that comprises by the insulating film of this method preparation.
Embodiment
The present invention is described now in more detail.
According to the present invention, prepare the organosilane oligopolymer of bridge joint from the organo-metallic silane compound of representing by following chemical formula 1, prepare the organic silicic acid ester polymer from this oligopolymer.The invention provides the composition that is used to form insulating film, this insulating film comprises organic silicon ester polymkeric substance, the invention provides the manufacture method of the semiconducter device insulating film that comprises organic silicon ester polymkeric substance and comprises the semiconducter device of insulating film.
Organic silicic acid ester polymer prepared in accordance with the present invention if be applied on the insulating film of semiconducter device, has excellent insulating property, film uniformity, dielectric properties, anti-crack property and physical strength.
Following reaction formula is an organic silicic acid ester polymer preparation method's of the present invention example.
First preparation method follows following reaction formula 1.
Reaction formula 1:
As directed, the grignard reaction of independent chemical formula 1 organo-metallic silane compound prepares the silane low polymer of carbon bridge joint, wherein removes the metallic compound by product.The silane low polymer of carbon bridge joint is dissolved in organic solvent, to wherein adding entry and catalyzer to cause that hydrolysis and condensation are with preparation organic silicic acid ester polymer.Equally, in organic solvent, mix silane low polymer and the silane compound or the silane low polymer of carbon bridge joint, to wherein adding entry and catalyzer to cause that hydrolysis and condensation are with preparation organic silicic acid ester polymer.
Second preparation method follows following reaction formula 2.
Reaction formula 2:
Grignard reaction between chemical formula 1 organo-metallic silane compound and silane compound or silane low polymer prepares the silane low polymer of carbon bridge joint.The silane low polymer of carbon bridge joint is dissolved in organic solvent, to wherein adding entry and catalyzer to cause that hydrolysis and condensation are with preparation organic silicic acid ester polymer.The silane low polymer and silane compound or the silane low polymer that mix the carbon bridge joint equally then in organic solvent are to wherein adding entry and catalyzer to cause that hydrolysis and condensation are with preparation organic silicic acid ester polymer.
The starting material that are used to prepare organic silicic acid ester polymer of the present invention are the organo-metallic silane compounds that satisfy chemical formula 1.The organo-metallic silane compound is preparation in the following way preferably:
A) in reaction vessel, introduce metal and dry it;
B) in container, add organic solvent and satisfy the organo-metallic silane compound of above chemical formula 1 with preparation to react them by the silane compound of following chemical general formula 2 expressions.
Chemical general formula 2:
R
1 pR
2 3-pSiR
3X
(wherein
R
1Be that hydrogen, fluorine, aryl, vinyl, allyl group or fluorine replace independently or unsubstituted linearity or branching C
1-4Alkyl;
R
2Be chlorine, acetoxyl group, hydroxyl or linearity or branching C independently
1-4Alkoxyl group;
R
3Be C
1-6Hydrocarbon;
X is a halogen; With
P is the integer of 0-2.
For example, following reaction formula 3 is followed in the reaction between metal and organic silane compound.
Reaction formula 3:
That is, with the chlorine alkyl silane, the organic silane compound and the metal M g that satisfy above chemical general formula 2 react to prepare a kind of organo-metallic silane compound that satisfies chemical formula 1.
The silane compound that is used for preparing the described method of carbon bridge joint silane low polymer or final product organic silicic acid ester polymer comprises: comprise the organosilane monomer of silicon, carbon, oxygen and hydrogen, and can be from the organosilane oligopolymer of its preparation.Preferably, silane compound or its oligopolymer by following chemical general formula 3 expressions can be used for preparing carbon bridge joint silane low polymer or final product organic silicic acid ester polymer.
Chemical general formula 3:
R
4 qR
5 4-qSi
(wherein
R
4Be that hydrogen, fluorine, aryl, vinyl, allyl group or fluorine replace independently or unsubstituted linearity or branching C
1-4Alkyl;
R
5Be chlorine, acetoxyl group, hydroxyl or linearity or branching C independently
1-4Alkoxyl group;
Q is the integer of 0-3).
According to the present invention, in the presence of solvent with silane low polymer and silane compound or the silane low polymer hydrolysis and the condensation of carbon bridge joint, add entry and catalyzer simultaneously to obtain to have the organic silicic acid ester polymer of concrete molecular weight, therefore be used to form the composition of insulating film.
The solvent that is used for hydrolysis and condensation or is used for coating comprise can dissolved composition with any reagent or the reagent mixture of the homogenous fluid mixture that forms silane compound or silane low polymer and carbon bridge joint silane low polymer.Be used for solvent of the present invention and comprise, as an example, aliphatic hydrocrbon such as Skellysolve A, iso-pentane, normal hexane, isohexane, pure isooctane, hexanaphthene, methylcyclohexane etc.; Aromatic hydrocarbon such as benzene,toluene,xylene, trimethylbenzene, ethylbenzene, methyl-ethyl benzene etc.; Alcohol is as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, hexalin, methyl-cyclohexanol, glycerine etc.; Ether such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, ether, positive propyl ether, isopropyl ether, diglyme, diox, dimethyl dioxane, ethylene glycol monomethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, Propylene Glycol Dimethyl Ether etc.; Ester such as diethyl carbonate, methyl acetate, ethyl acetate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, glycol diacetate etc.; With acid amides such as N-Methyl pyrrolidone, methane amide, N-methylformamide, N-ethyl-formamide, N,N-dimethylacetamide, N, N-diethyl acetamide etc.
After reaction, remove all solvents of being used for hydrolysis and condensation with acquisition organic silicic acid ester polymer oil or powder, the organic silicic acid ester polymer dissolves in the organic solvent that is used to form film, and the organic solvent that perhaps is used for hydrolysis and condensation can be directly used in the formation film.Can use two or more organic solvents together.
The present invention uses catalyzer to promote hydrolysis and condensation.The catalyzer that is used for hydrolysis and condensation comprises acid catalyst, alkaline catalysts, metal-chelating compounds, salt catalyst etc.For example, acid catalyst comprises hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, Phenylsulfonic acid, toluenesulphonic acids, acetate, oxalic acid, propanedioic acid, toxilic acid, fumaric acid, citric acid, propionic acid etc.; Alkaline catalysts comprises ammonia, sodium hydroxide, calcium hydroxide, potassium hydroxide, Trimethylamine 99, triethylamine, diethanolamine, trolamine, dimethylethanolamine, monomethyl diethanolamine diazabicyclo undecylene, pyridine, pyrroles's piperidines, choline, tetramethyleneimine, piperazine etc.The metal-chelating compounds comprises organometallic compound that contains metal such as aluminium, titanium, zirconium, tin, tantalum etc.; Salt catalyst comprises conjugate acid and conjugate base compound such as ammonium acetate.Acid, alkali, metal-chelating compounds and salt catalyst can be used separately or being used in combination, and can use they two or more stage by stage.
The catalyst amounts that adds can be to promote bridge joint silane low polymer and the hydrolysis of silane compound or silane low polymer and any amount of condensation reaction, and the temperature of optimal number can depend on the chemical constitution of catalyzer and hydrolysis and condensation and carry out the time.Generally speaking, the Siliciumatom in per 1 mole of silane compound, the add-on of catalyzer is the 0.00001-1 mole, preferred 0.5 mole or littler.If the add-on of catalyzer surpasses the Siliciumatom in 1 mole of per 1 mole of silane compound, then speed of reaction can be very high and can be difficult to control molecular weight and may easily produces gel.
In the present invention, add entry to cause the hydrolysis of silane compound.The quantity of water is the 0.1-20 mole suitably, the Siliciumatom in the preferred per 1 mole of silane compound of 1-10 mole, and it can add stage by stage or add continuously.Catalyzer can join in the organic solvent in advance, and maybe it can dissolve or disperse when adding entry.
In the time will making product have required molecular weight, temperature of reaction is had no particular limits.Temperature can preferably not be higher than the boiling point of the organic solvent of use, and can be preferably 0 ℃-100 ℃ molecular weight with the hydrolysate of control acquisition.In hydrolysis with under the condensation time reaction times is had no particular limits, reaction can be finished under product reaches time of described molecular weight.Usually the molecular weight that preferably sets final product is the 500-1 of weight-average molecular weight, and 000,000 to form uniform paint film.
By adopting organic solvent dissolution to prepare the coating composition that the present invention is used to form insulating film by the organic silicic acid ester polymer of above method preparation.As required, various additives can join in the composition that is used to form the set amount insulating film according to its purpose as organic molecule, organic polymer, organic branch-shape polymer, colloid silica, aerosol, dried colloidal sol and tensio-active agent etc.
In solids content dissolved scope, can select solid content concentration the solution from the angle of required viscosity of solution or paint film thickness suitably.The solids concn of the present composition is 2-60wt% generally speaking, preferred 5-40wt%.
By at substrate such as silicon wafer, SiO
2Wafer, SiN wafer, semiconductor compound etc. are gone up the coating coating insulating film composition and are formed insulating film of the present invention.Can form insulating film by standard method such as spin coated, the coating of flowing, dip-coating and spray coating.When on the interbed dielectric film that composition of the present invention is coated to semiconducter device, rotary coating method preferably, this is because distribution meeting so be uniform in the plane of film thickness.
The thickness of the viscosity that can be by changing composition and the speed of rotation controlling diaphragm of spin coated device, for the interlayer insulating film of semiconducter device multilayer circuit, 0.2-2 μ m is suitable.
Can form organic silicic acid ester polymer insulating film by drying after coated technique and curing (sclerosis) technology with three-dimensional structure.Normally, under 30-250 ℃ and 300-600 ℃, carry out drying and curing respectively, preferably under 350-500 ℃, be cured especially.If solidification value surpasses 600 ℃, the thermostability of organic silicic acid ester polymer can reduce, if it is less than 300 ℃, because the polycondensation of organic silicic acid ester polymer also not exclusively takes place, film strength can reduce, and because the existence of remaining functional group, dielectric properties can reduce.
Dry and curing process can carry out the while continuously with concrete speed elevated temperature, or they can carry out stage by stage.If carry out stage by stage, dry and curing process carried out respectively 1 minute and 5 hours suitably.Can use hot plate, baking oven, process furnace etc., at inert gas environment such as nitrogen or argon gas, helium environment, (for example, air under) the oxygen atmosphere, vacuum or under ammonia and hydrogen-containing gas environment heats as adopting oxygen-containing gas.Drying can be carried out by identical heating means or by different heating means with solidifying.
After curing process,, can carry out surface treatment to minimize the hydroxyl quantity in the insulating film by usual method as needs.Carry out surface treatment in the following way to remove residual hydroxy groups: varnished insulation film in silane compound solution such as hexamethyldisilazane, alkyl chlorosilane and alkyl acetoxysilane, with cause therebetween reaction and dry it, or, under 300-600 ℃, add opaque film 1 minute or longer by under reducing gas environment such as hydrogen or fluoro-gas atmosphere.
Because it has excellent insulating property, film uniformity, dielectric properties, anti-crack property and physical strength, be used for the interlayer insulating film of the semiconducter device of LSI, system LSI, DRAM, SDRAM, D-RDRAM etc. suitably by the film of this method acquisition; Protective membrane is as being used for the topcoating film of semiconducter device; The interlayer insulating film that is used for the multilayer wiring substrate; With protective membrane that is used for the liquid display equipment or insulating protective film.
With reference now to following embodiment and Comparative Examples, explain the present invention in more detail.Yet these embodiment are used to illustrate the present invention, but the present invention is not limited to these embodiment.
Embodiment:
Embodiment 1:
(preparation of the organo-metallic silane compound of representing by chemical formula 1)
In reactor, introduce 0.71g magnesium and dry after it, to wherein adding 15ml solvent distillatory tetrahydrofuran (THF) (THF).The temperature of mixture is reduced to 0 ℃, with 5g chloromethyl triethoxyl silane, satisfy the organic silane compound of chemical general formula 2, slowly adds with reaction and confirm by NMR up to preparation Grignard reagent and reaction.
(preparation of carbon bridge joint oligopolymer)
After initial reaction was finished, reaction continued 12 hours to form the oligopolymer of carbon bridge joint.Adopt celite to filter to wherein adding the 50ml hexane with the precipitation magnesium salts and with throw out then, in vacuum drying oven, remove organic solvent then fully to obtain product.
(preparation of organic silicic acid ester polymer)
Product and 4.64g methyltrimethoxy silane that mixing 1.5g obtains in the 11.3ml tetrahydrofuran solvent and the organic silane compound that satisfies chemical general formula 3.
The temperature of mixture is reduced to 0 ℃, 1.78ml distilled water and 0.21ml catalyzer, 2N salt slow acid are joined wherein to react 30 minutes.Then, temperature slowly is elevated to 80 ℃ and will react and continue 16 hours reflux simultaneously.After reaction, mixture adopted diethylether solvent dilution and adopt distilled water wash 3-4 time to become neutrality up to acidity.In vacuum drying oven, remove remaining solvent fully to obtain solid (powder) product from the organic layer that obtains.
(preparation of insulating film)
It is 1.5g to set total solution weight that the powder that 300mg is obtained is dissolved in methyl iso-butyl ketone (MIBK).Remove impurity and spin coated solution to obtain film by strainer from the solution that obtains.By drying and curing process, keep temperature 1 hour and the preparation insulating film at elevated temperature to 430 under the speed of 2 ℃ of per minutes ℃ and under nitrogen environment.
Embodiment 2:
(preparation of the organo-metallic silane compound of representing by chemical formula 1)
In reactor, introduce 0.71g magnesium and dry after it, to wherein adding 15ml solvent distillatory tetrahydrofuran (THF) (THF).The temperature of mixture is reduced to 0 ℃, with 0.2g methylene dichloride and 0.2g chloromethyl triethoxyl silane, satisfy the organic silane compound of chemical general formula 2, slowly joins wherein.In the time will beginning to produce Grignard reagent, with 4.8g chloromethyl triethoxyl silane, satisfy the organic compound of chemical general formula 2, further slowly add with the preparation Grignard reagent, reaction is confirmed by NMR.
(preparation of carbon bridge joint oligopolymer)
5.37g tetramethoxy-silicane, the compound that satisfies chemical general formula 3 and 15ml tetrahydrofuran (THF) are slowly joined in the above solution and with mixture to descend to stir 2 hours at 0 ℃.To wherein adding the 50ml hexane, adopt celite to filter throw out with the precipitation magnesium salts.In vacuum drying oven, therefrom remove organic solvent then fully to obtain the silane low polymer product of carbon bridge joint.
(preparation of organic silicic acid ester polymer)
Carbon bridge joint silane low polymer and the 18.17g methyltrimethoxy silane that mixing 44.2g obtains in the 30ml tetrahydrofuran solvent, the organic silane compound that satisfies chemical general formula 3.
The temperature of mixture is reduced to 0 ℃, 8.0ml distilled water and 0.98ml catalyzer, 5N salt slow acid are joined wherein to react 30 minutes.Then, temperature slowly is elevated to 80 ℃ and also will reacts lasting 16 hours reflux simultaneously.After reaction, mixture adopted diethylether solvent distillation and adopt distilled water wash 3-4 time to become neutrality up to acidity.In vacuum drying oven, remove remaining solvent fully to obtain solid (powder) product from the organic layer that obtains.
(preparation of insulating film)
By powder dry as method identical among the embodiment 1 and that curing obtains, preparation insulating film.
Embodiment 3:
(preparation of organic silicic acid ester polymer)
In the 60ml tetrahydrofuran solvent, mix carbon bridge joint silane low polymer, 30.0g methyltrimethoxy silane and the 3.4g tetramethoxy-silicane that 9g is obtained by same procedure among the embodiment 1.
The temperature of mixture is reduced to 0 ℃, 37ml catalyzer, 0.01N nitric acid are slowly joined wherein to react 30 minutes.Then, temperature slowly is elevated to 70 ℃ and also will reacts lasting 16 hours reflux simultaneously.After reaction, mixture adopted diethylether solvent dilution and adopt distilled water wash 3-4 time to become neutrality up to acidity.In vacuum drying oven, remove remaining solvent fully to obtain solids content from the organic layer that obtains.
(preparation of insulating film)
By powder dry as method identical among the embodiment 1 and that curing obtains, preparation insulating film.
Comparative Examples 1:
7.26g methyltrimethoxy silane, organic silane compound and 4.05ml distilled water are mixed in 10ml tetrahydrofuran (THF) (THF) solvent, and under nitrogen environment to the 2N hydrochloric acid that wherein slowly adds 0.80ml.
At room temperature react them after 30 minutes, slowly increase temperature and will react and continue 24 hours whiles reflux.
After reaction, the temperature of solution is reduced to room temperature, and solution is adopted the diethylether solvent dilution and adopt water washing 3-4 time to become neutrality up to acidity.Sal epsom is incorporated in the organic layer of acquisition therefrom to remove remainder water fully.In vacuum drying oven, remove fully and desolvate to obtain solid (powder) product from the organic layer that obtains.
(preparation of insulating film)
By powder dry as method identical among the embodiment 1 and that sclerosis obtains, preparation insulating film.
By the following method a)-c) measure at embodiment 1,2,3 and Comparative Examples 1 in the physicals of organic silicic acid ester polymer of preparation, to obtain to be shown in the result of table 1.
A) molecular weight (quality molecular-weight average: Mw)-the average molecular numerical quantity that uses polystyrene to obtain by gel permeation chromatography (GPC) as standard substance.
B) spin coated of the mechanical property of film-on 2 * 2 inches Si wafers and under 430 ℃ at N
2Environment sclerosis was down measured after 1 hour.
I) Tribolndenter of hardness-use Hysitron Inc measures.
Whether ii) anti-crack property-preparation 1 μ m film to observe the crack takes place.
C) dielectric properties of film-making MIM (metal/insulator/semi-conductor) device on the Si wafer and under 1MHz, using the LCR table of HP Company to measure dielectric properties.
The results are shown in Table 1.
Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | |
Mw | 11807 | 27716 | 3100 | 11000 |
Hardness | 0.62 | 0.58 | 1.1 | 0.32 |
Anti-crack property | 2.4E12 | 5.3E-12 | 1.2E-12 | 1.3E-9 |
Specific inductivity | 2.78 | 2.75 | 2.83 | 2.73 |
Table 1
As shown in table 1, from the film of organic silicic acid ester polymer of the present invention manufacturing excellent dielectric properties and improved physical strength and anti-crack property are arranged.
Organic silicic acid ester polymer prepared in accordance with the present invention is heat-staple and has good film forming properties, excellent physical strength and anti-crack property have excellent insulating property, film uniformity, dielectric properties, anti-crack property and physical strength from the film of its manufacturing.
Claims (9)
1. the preparation method of an organic silicic acid ester polymer comprises the steps:
A) provide the organo-metallic silane compound of representing by following chemical formula 1;
B) cause the grignard reaction of following material:
I) independent a) organo-metallic silane compound, or
Ii) a) organo-metallic silane compound and silane compound or silane low polymer,
With the silane low polymer of preparation carbon bridge joint and remove the metallic compound by product;
C) in organic solvent, mix b) silane low polymer of carbon bridge joint, to wherein adding entry and catalyzer to cause that hydrolysis and condensation are with preparation organic silicic acid ester polymer;
Chemical formula 1:
R
1 PR
2 3-pSiR
3MX
Wherein
R
1Be that hydrogen, fluorine, aryl, vinyl, allyl group or fluorine replace independently or unsubstituted linearity or branching C
1-4Alkyl;
R
2Be chlorine, acetoxyl group, hydroxyl or linearity or branching C independently
1-4Alkoxyl group;
R
3Be C
1-6Alkyl;
M is magnesium, mercury or copper;
X is a halogen;
P is the integer of 0-2.
2. according to the preparation method of the organic silicic acid ester polymer of claim 1, wherein prepare a) organo-metallic silane compound in the following way:
I) in reaction vessel, introduce metal and dry it;
Ii) in reaction vessel, add organic solvent and by the silane compound of following chemical general formula 2 expressions and react them:
Chemical general formula 2:
R
1 PR
2 3-pSiR
3X
Wherein
R
1Be that hydrogen, fluorine, aryl, vinyl, allyl group or fluorine replace independently or unsubstituted linearity or branching C
1-4Alkyl;
R
2Be chlorine, acetoxyl group, hydroxyl or linearity or branching C independently
1-4Alkoxyl group;
R
3Be C
1-6Alkyl;
X is a halogen;
P is the integer of 0-2.
3. according to the preparation method of the organic silicic acid ester polymer of claim 1, b wherein) silane compound ii) or silane low polymer are silane compound or its oligopolymer by following chemical general formula 3 expressions:
Chemical general formula 3:
R
4 qR
5 4-qSi
Wherein
R
4Be that hydrogen, fluorine, aryl, vinyl, allyl group or fluorine replace independently or unsubstituted linearity or branching C
1-4Alkyl;
R
5Be chlorine, acetoxyl group, hydroxyl or linearity or branching C independently
1-4Alkoxyl group;
Q is the integer of 0-3.
4. organic silicic acid ester polymer that is prepared by a method comprising the following steps:
A) provide the organo-metallic silane compound of representing by following chemical formula 1;
B) cause the grignard reaction of following material:
I) independent a) organo-metallic silane compound, or
Ii) a) organo-metallic silane compound and silane compound or silane low polymer,
With the silane low polymer of preparation carbon bridge joint and remove the metallic compound by product;
C) in organic solvent, mix b) silane low polymer of carbon bridge joint, to wherein adding entry and catalyzer to cause that hydrolysis and condensation are with preparation organic silicic acid ester polymer;
Chemical formula 1:
R
1 PR
2 3-pSiR
3MX
Wherein
R
1Be that hydrogen, fluorine, aryl, vinyl, allyl group or fluorine replace independently or unsubstituted linearity or branching C
1-4Alkyl;
R
2Be chlorine, acetoxyl group, hydroxyl or linearity or branching C independently
1-4Alkoxyl group;
R
3Be C
1-6Alkyl;
M is magnesium, mercury or copper;
X is a halogen;
P is the integer of 0-2.
5. composition that is used to form the insulating film of semiconducter device comprises:
A) the organic silicic acid ester polymer for preparing by the method that comprises the steps:
I) provide the organo-metallic silane compound of representing by following chemical formula 1;
Ii) cause the grignard reaction of following material:
Independent i) organo-metallic silane compound, or
I) organo-metallic silane compound and silane compound or silane low polymer,
With the silane low polymer of preparation carbon bridge joint and remove the metallic compound by product;
Iii) in organic solvent, mix the ii) silane low polymer of carbon bridge joint, to wherein adding entry and catalyzer to cause that hydrolysis and condensation are with preparation organic silicic acid ester polymer; With
B) organic solvent;
Chemical formula 1:
R
1 PR
2 3-pSiR
3MX
Wherein
R
1Be that hydrogen, fluorine, aryl, vinyl, allyl group or fluorine replace independently or unsubstituted linearity or branching C
1-4Alkyl;
R
2Be chlorine, acetoxyl group, hydroxyl or linearity or branching C independently
1-4Alkoxyl group;
R
3Be C
1-6Alkyl;
M is magnesium, mercury or copper;
X is a halogen;
P is the integer of 0-2.
6. according to the composition of the insulating film that is used to form semiconducter device of claim 5, further comprise:
C) one or more are selected from following additive: organic polymer, organic branch-shape polymer, colloid silica and tensio-active agent.
7. a method of making the semiconducter device insulating film comprises the steps:
A) coating comprises i on the substrate of semiconducter device) the described organic silicic acid ester polymer of claim 4 and the ii) composition of organic solvent; With
B) the dry composition that applies with curing.
8. according to the method for the manufacturing semiconducter device insulating film of claim 7, wherein a) composition comprises that further one or more are selected from following additive: organic polymer, organic branch-shape polymer, colloid silica and tensio-active agent.
9. a semiconducter device comprises insulating film, and this insulating film is prepared by the method that comprises the steps:
A) coating comprises i on the substrate of semiconducter device) the described organic silicic acid ester polymer of claim 4 and the ii) composition of organic solvent; With
B) the dry composition that applies with curing.
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KR31816/2001 | 2001-06-07 | ||
KR10-2001-0031816A KR100451044B1 (en) | 2001-06-07 | 2001-06-07 | Method for preparing organic silicate polymer and method for preparing insulating film using the same |
KR31816/01 | 2001-06-07 |
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US (2) | US6933360B2 (en) |
EP (1) | EP1392761A1 (en) |
JP (1) | JP3819391B2 (en) |
KR (1) | KR100451044B1 (en) |
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WO (1) | WO2002098955A1 (en) |
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KR100451044B1 (en) * | 2001-06-07 | 2004-10-02 | 주식회사 엘지화학 | Method for preparing organic silicate polymer and method for preparing insulating film using the same |
KR100422916B1 (en) * | 2001-06-26 | 2004-03-12 | 주식회사 엘지화학 | Organic silicate polymer and low dielectric insulation film comprising the same |
KR100508903B1 (en) * | 2002-05-06 | 2005-08-17 | 주식회사 엘지화학 | Composition for low dielectric film and method for forming low dielectric film |
WO2005068539A1 (en) | 2004-01-16 | 2005-07-28 | Jsr Corporation | Method for producing polymer, polymer, composition for forming insulating film, method for producing insulating film, and insulating film |
TW200538491A (en) * | 2004-01-16 | 2005-12-01 | Jsr Corp | The composition of forming insulating film and the method of producing insulating film |
KR20070010011A (en) | 2004-02-26 | 2007-01-19 | 제이에스알 가부시끼가이샤 | Polymer and process for producing the same, composition for forming insulating film, and insulating film and method of forming the same |
JP5110238B2 (en) * | 2004-05-11 | 2012-12-26 | Jsr株式会社 | Insulating film forming composition and method for producing the same, and silica-based insulating film and method for forming the same |
JP5110239B2 (en) * | 2004-05-11 | 2012-12-26 | Jsr株式会社 | Method for forming organic silica film, composition for film formation |
WO2005108469A1 (en) * | 2004-05-11 | 2005-11-17 | Jsr Corporation | Method for forming organic silica film, organic silica film, wiring structure, semiconductor device, and composition for film formation |
ATE543211T1 (en) * | 2005-09-01 | 2012-02-15 | Freescale Semiconductor Inc | CUT LAYER FORMATION ON A DOUBLE DAMASCENE CONNECTOR |
KR100955570B1 (en) * | 2006-09-18 | 2010-04-30 | 주식회사 엘지화학 | At low temperature, fast hardening composition for preparing protecting film prepared therefrom, and substrate comprising the same |
KR101872684B1 (en) * | 2014-04-08 | 2018-06-29 | (주)필스톤 | Insulation coating composition and manufacturing method thereof |
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GB591149A (en) * | 1944-11-30 | 1947-08-08 | John Edward Hackford | Improvements in or relating to the production of organo-silicon compounds by the grignard reaction |
US5302734A (en) * | 1991-06-14 | 1994-04-12 | Korea Institute Of Science And Technology | 1,3-disilacyclobutanes and the method for producing thereof |
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US5912313A (en) * | 1995-11-22 | 1999-06-15 | The B. F. Goodrich Company | Addition polymers of polycycloolefins containing silyl functional groups |
JPH1116904A (en) * | 1997-06-26 | 1999-01-22 | Mitsubishi Electric Corp | Semiconductor device and manufacture thereof |
US6140445A (en) * | 1998-04-17 | 2000-10-31 | Crompton Corporation | Silane functional oligomer |
EP1790703B1 (en) * | 1998-04-24 | 2014-07-30 | JGC Catalysts and Chemicals Ltd. | Coating liquid for forming silica-based film having low dielectric constant and substrate having film of low dielectric constant coated thereon |
US6147009A (en) * | 1998-06-29 | 2000-11-14 | International Business Machines Corporation | Hydrogenated oxidized silicon carbon material |
JP4305587B2 (en) | 1999-04-27 | 2009-07-29 | Jsr株式会社 | Materials for forming interlayer insulation film for semiconductor devices |
US6107357A (en) * | 1999-11-16 | 2000-08-22 | International Business Machines Corporatrion | Dielectric compositions and method for their manufacture |
KR100425242B1 (en) * | 2000-05-29 | 2004-03-30 | 주식회사 엘지화학 | Dielectrics material for layer of semiconductor and semiconductor device using the same |
KR100405312B1 (en) * | 2001-04-11 | 2003-11-12 | 주식회사 엘지 | Organic silicate polymer and low dielectric insulation film comprising the same |
KR100451044B1 (en) * | 2001-06-07 | 2004-10-02 | 주식회사 엘지화학 | Method for preparing organic silicate polymer and method for preparing insulating film using the same |
-
2001
- 2001-06-07 KR KR10-2001-0031816A patent/KR100451044B1/en active IP Right Grant
-
2002
- 2002-05-13 EP EP02776539A patent/EP1392761A1/en not_active Withdrawn
- 2002-05-13 US US10/332,452 patent/US6933360B2/en not_active Expired - Lifetime
- 2002-05-13 WO PCT/KR2002/000888 patent/WO2002098955A1/en active Application Filing
- 2002-05-13 CN CNB028018273A patent/CN100422240C/en not_active Expired - Fee Related
- 2002-05-13 JP JP2003502073A patent/JP3819391B2/en not_active Expired - Lifetime
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2005
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB591149A (en) * | 1944-11-30 | 1947-08-08 | John Edward Hackford | Improvements in or relating to the production of organo-silicon compounds by the grignard reaction |
US5302734A (en) * | 1991-06-14 | 1994-04-12 | Korea Institute Of Science And Technology | 1,3-disilacyclobutanes and the method for producing thereof |
Also Published As
Publication number | Publication date |
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EP1392761A1 (en) | 2004-03-03 |
US7238627B2 (en) | 2007-07-03 |
US20030181750A1 (en) | 2003-09-25 |
KR20020094098A (en) | 2002-12-18 |
WO2002098955A1 (en) | 2002-12-12 |
US20050266699A1 (en) | 2005-12-01 |
KR100451044B1 (en) | 2004-10-02 |
JP3819391B2 (en) | 2006-09-06 |
CN1463279A (en) | 2003-12-24 |
JP2004533517A (en) | 2004-11-04 |
US6933360B2 (en) | 2005-08-23 |
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